Synergistic mixtures for fungal controls in cereals

ABSTRACT

A fungicidal composition containing a fungicidally effective amount of the compound of Formula I, (S)-1,1-bis(4-fluorophenyl)propan-2-yl (3-acetoxy-4-methoxypicolinoyl)-L-alaninate, and at least one fungicide selected from the group consisting of epoxiconazole, prothioconazole, azoxystrobin, pyraclostrobin, fluxapyroxad, benzovindiflupyr, and chlorothalonil, provides synergistic control of selected fungi.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.16/610,119, filed on Nov. 1, 2019, which was a national stage entry ofPCT Patent Application Serial No. PCT/US18/030559, filed on May 2, 2018,which claims the benefit of U.S. Provisional Patent Application Ser. No.62/500,199 filed May 2, 2017, which is expressly incorporated byreference herein.

FIELD

This disclosure concerns a synergistic fungicidal composition containing(a) the compound of Formula I and (b) at least one fungicide selectedfrom the group consisting of a sterol biosynthesis inhibitor, forexample prothioconazole, epoxiconazole, cyproconazole, myclobutanil,metconazole, difenoconazole, tebuconazole, tetraconazole, fenbuconazole,propiconazole, fluquinconazole, flusilazole, and flutriafol; astrobilurin, for example pyraclostrobin, fluoxastrobin, azoxystrobin,trifloxystrobin, picoxystrobin, and kresoxim methyl; a succinatedehydrogenase inhibitor, for example fluxapyroxad, benzovindiflupyr,penthiopyrad, isopyrazam, bixafen, boscalid, penflufen, and fluopyram; amulti-site inhibitor, for example chlorothalonil, or other commercialfungicides to provide control of any plant fungal pathogen.

BACKGROUND AND SUMMARY

Fungicides are compounds, of natural or synthetic origin, which act toprotect plants against damage caused by fungi. Current methods ofagriculture rely heavily on the use of fungicides. In fact, some cropscannot be grown usefully without the use of fungicides. Using fungicidesallows a grower to increase the yield and the quality of the crop, andconsequently, increase the value of the crop. In most situations, theincrease in value of the crop is worth at least three times the cost ofthe use of the fungicide.

However, no one fungicide is useful in all situations and repeated usageof a single fungicide frequently leads to the development of resistanceto that and related fungicides. Consequently, research is beingconducted to produce fungicides and combinations of fungicides that aresafer, that have better performance, that require lower dosages, thatare easier to use, and that cost less.

Synergism occurs when the activity of two or more compounds exceeds theactivities of the compounds when used alone.

It is an object of this disclosure to provide synergistic compositionscomprising fungicidal compounds. It is a further object of thisdisclosure to provide processes that use these synergistic compositions.The synergistic compositions are capable of preventing or curing, orboth, diseases caused by fungi of the classes Ascomycetes andBasidiomycetes. In addition, the synergistic compositions have improvedefficacy against the Ascomycete and Basidiomycete pathogens, includingbarley scald. In accordance with this disclosure, synergisticcompositions are provided along with methods for their use.

DETAILED DESCRIPTION

The present disclosure concerns a synergistic fungicidal mixturecomprising a fungicidally effective amount of (a) the compound ofFormula I and (b) at least one fungicide selected from the compounds ofthe following groups A.1, B.1 and C.1:

A.1 Sterol biosynthesis inhibitors (SBI fungicides) selected from thefollowing groups a), b) and c):

a) C14 demethylase inhibitors (DMI fungicides), for exampleprothioconazole, epoxiconazole, cyproconazole, myclobutanil,metconazole, difenoconazole, tebuconazole, tetraconazole, fenbuconazole,propiconazole, fluquinconazole, flusilazole, flutriafol and prochloraz;

b) Delta 14-reductase inhibitors, for example, fenpropimorph andaldimorph;

c) Inhibitors of 3-keto reductase such as fenhexamid;

B.1 Respiration inhibitors selected from the following groups a) and b):

a) inhibitors of complex II (SDHI fungicides, e.g. carboxamides), forexample fluxapyroxad, benzovindiflupyr, penthiopyrad, isopyrazam,bixafen, boscalid, penflufen, and fluopyram;

b) inhibitors of complex III at the Q_(o) site (e.g. strobilurins), forexample pyraclostrobin, fluoxastrobin, azoxystrobin, trifloxystrobin,picoxystrobin, and kresoxim methyl;

C.1 Inhibitors with multi-site action selected from the following groupsa) and b):

a) thio- and dithiocarbamates, such as mancozeb;

b) organochlorine compounds (e.g. phthalimides, sulfamides,chloronitriles) such as chlorothalonil;

or other commercial fungicides to provide control of any plant fungalpathogen.

As used herein, the compound of Formula I is(S)-1,1-bis(4-fluorophenyl)propan-2-yl(3-acetoxy-4-methoxypicolinoyl)-L-alaninate. The compound of Formula Iprovides control of a variety of pathogens in economically importantcrops including, but not limited to, the causal agent of barley scald,Rhynchosporium secalis (RHYNSE).

As used herein, epoxiconazole is the common name for(2RS,3SR)-1-[3-(2-chlorophenyl)-2,3-epoxy-2-(4-fluorophenyl)propyl]-1H-1,2,4-triazoleand possesses the following structure:

Its fungicidal activity is described in The Pesticide Manual, FifteenthEdition, 2009. Epoxiconazole provides broad spectrum control, withpreventive and curative action, of diseases caused by Ascomycetes,Basidiomycetes and Deuteromycetes in bananas, cereals, coffee, rice andsugar beet.

As used herein, prothioconazole is the common name for2-[(2RS)-2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2H-1,2,4-triazole-3(4H)-thioneand possesses the following structure:

Its fungicidal activity is described in The Pesticide Manual, FifteenthEdition, 2009. Prothioconazole provides control of diseases such aseyespot (Pseudocercosporella herpotrichoides), Fusarium ear blight(Fusarium spp., Microdochium nivale), leaf blotch diseases (Zymoseptoriatritici, Parastagonospora nodorum, Pyrenophora spp., Rhynchosporiumsecalis, etc.), rust (Puccinia spp.) and powdery mildew (Blumeriagraminis), by foliar application, in wheat, barley and other crops.

As used herein, azoxystrobin is the common name for(E)-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylateand possesses the following structure:

Its fungicidal activity is exemplified in The e-Pesticide Manual,Version 5.2, 2011. Exemplary uses of azoxystrobin include, but are notlimited to, control of the following pathogens: Erysiphe graminis,Puccinia spp., Parastagonospora nodorum, Zymoseptoria tritici andPyrenophora teres on temperate cereals; Pyricularia oryzae andRhizoctonia solani on rice; Plasmopara viticola and Uncinula necator onvines; Sphaerotheca fuliginea and Pseudoperonospora cubensis oncucurbitaceae; Phytophthora infestans and Alternaria solani on potatoand tomato; Mycosphaerella arachidis, Rhizoctonia solani and Sclerotiumrolfsii on peanut; Monilinia spp. and Cladosporium carpophilum on peach;Pythium spp. and Rhizoctonia solani on turf; Mycosphaerella spp. onbanana; Cladosporium caryigenum on pecan; Elsinoe fawcettii,Colletotrichum spp. and Guignardia citricarpa on citrus; Colletotrichumspp. and Hemileia vastatrix on coffee.

As used herein, pyraclostrobin is the common name for methylN-[2-[[[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy]methyl]phenyl]-N-methoxycarbamateand possesses the following structure:

Its fungicidal activity is described in BCPC Online PesticideManual—Latest Version. Exemplary uses of pyraclostrobin include, but arenot limited to, broad spectrum disease control of major plant pathogens,including Zymoseptoria tritici, Puccinia spp., Drechsleratritici-repentis, Pyrenophora teres, Rhynchosporium secalis and Septorianodorum in cereals; Mycosphaerella spp. in peanuts; Septoria glycines,Cercospora kikuchii and Phakopsora pachyrhizi in soybeans; Plasmoparaviticola and Erysiphe necator in grapes; Phytophthora infestans andAlternaria solani in potatoes and tomatoes; Sphaerotheca fuliginea andPseudoperonospora cubensis in cucumber; Mycosphaerella fijiensis inbananas; Elsinoe fawcettii and Guignardia citricarpa in citrus andRhizoctonia solani and Pythium aphanidermatum in turf.

As used herein, fluxapyroxad is the common name for3-(difluoromethyl)-1-methyl-N-(3′,4′,5′-trifluorobiphenyl-2-yl)pyrazole-4-carboxamideand possesses the following structure:

Its fungicidal activity is exemplified in Agrow Intelligence(https://www.agra-net.net/agra/agrow/databases/agrow-intelligence/).Exemplary uses of fluxapyroxad include, but are not limited to, thecontrol of plant pathogens, such as Helminthosporium teres (net blotch),Rhynchosporium secalis (leaf scald), Puccinia hordei (brown rust), andErysiphe graminis f.sp. hordei (powdery mildew) in a range of crops,such as barley, maize, and soybeans.

As used herein, benzovindiflupyr is the common name forN-[(1RS,4SR)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methylpyrazole-4-carboxamideand possesses the following structure:

Its fungicidal activity is exemplified in Agrow Intelligence(https://www.agra-net.net/agra/agrow/databases/agrow-intelligence/).Exemplary uses of benzovindiflupyr include, but are not limited to,controlling a variety of pathogens such as Botrytis spp., Erysiphe spp.,Rhizoctonia spp., Septoria spp., Phytophthora spp., Pythium spp.,Phakopsora pachyrhizi, and Puccinia recondita, in a range of cropsincluding vines, cereals, soybeans, cotton, and fruit and vegetablecrops.

As used herein, chlorothalonil is the common name fortetrachloroisophthalonitrile and possesses the following structure:

Its fungicidal activity is described in The Pesticide Manual, FifteenthEdition, 2009. Chlorothalonil provides control of many fungal diseasesin a wide range of crops, including pome fruit, stone fruit, almonds,citrus fruit, bush and cane fruit, cranberries, strawberries, pawpaws,bananas, mangoes, coconut palms, oil palms, rubber, pepper, vines, hops,vegetables, cucurbits, tobacco, coffee, tea, rice, soya beans, peanuts,potatoes, sugar beet, cotton, maize, ornamentals, mushrooms, and turf.

In the compositions described herein, the concentration ratio of themixture of the compound of Formula I to other fungicides at which thefungicidal effect is synergistic against barley scald caused byRhynchosporium secalis (RHYNSE) in protectant applications lies withinthe range from about 26:1 to about 1:64.

In the compositions described herein, the concentration ratio of themixture of the compound of Formula I to a sterol biosynthesis inhibitorat which the fungicidal effect is synergistic against RHYNSE inprotectant applications lies within the range from about 16:1 to about1:1. In one embodiment, the concentration ratio of the mixture of thecompound of Formula I to epoxiconazole at which the fungicidal effect issynergistic against RHYNSE in protectant applications is about 16:1. Inanother embodiment, the concentration ratio of the mixture of thecompound of Formula I to prothioconazole at which the fungicidal effectis synergistic against RHYNSE in protectant applications is about 1:1.

In the compositions described herein, the concentration ratio of themixture of the compound of Formula I to a strobilurin fungicide at whichthe fungicidal effect is synergistic against RHYNSE in protectantapplications lies within the range from about 26:1 to about 1:16. In oneembodiment, the concentration ratio of the mixture of the compound ofFormula I to azoxystrobin at which the fungicidal effect is synergisticagainst RHYNSE in protectant applications lies within the range fromabout 1:1 to about 1:16. In another embodiment, the concentration ratioof the mixture of the compound of Formula I to pyraclostrobin at whichthe fungicidal effect is synergistic against RHYNSE in protectantapplications lies within the range from about 26:1 to about 1.6:1.

In the compositions described herein, the concentration ratio of themixture of the compound of Formula I to a succinate dehydrogenaseinhibitor (SDHI) fungicide at which the fungicidal effect is synergisticagainst RHYNSE in protectant applications lies within the range fromabout 26:1 to about 1:1.3. In one embodiment, the concentration ratio ofthe mixture of the compound of Formula I to fluxapyroxad at which thefungicidal effect is synergistic against RHYNSE in protectantapplications lies within the range from about 26:1 to about 6.5:1. Inanother embodiment, the concentration ratio of the mixture of thecompound of Formula I to benzovindiflupyr at which the fungicidal effectis synergistic against RHYNSE in protectant applications is about 1:1.3.

In the compositions described herein, the concentration ratio of themixture of the compound of Formula I to chlorothalonil at which thefungicidal effect is synergistic against RHYNSE in protectantapplications lies within the range from about 1:8 to about 1:64.

The rate at which the synergistic composition is applied will dependupon the particular type of fungus to be controlled, the degree ofcontrol required and the timing and method of application. In general,the compositions described herein can be applied at an application rateof between about 35 grams per hectare (g/ha) and about 2600 g/ha basedon the total amount of active ingredients in the composition.

The compositions comprising the compound of Formula I and a sterolbiosynthesis inhibitor can be applied at an application rate of betweenabout 60 g/ha and about 350 g/ha based on the total amount of activeingredients in the composition. Epoxiconazole is applied at a rate ofbetween about 50 g/ha and about 250 g/ha and the compound of Formula Iis applied at a rate between about 10 g/ha and about 100 g/ha.Prothioconazole is applied at a rate of between about 50 g/ha and about250 g/ha and the compound of Formula I is applied at a rate betweenabout 10 g/ha and about 100 g/ha.

The compositions comprising the compound of Formula I and a strobilurinfungicide can be applied at an application rate of between about 60 g/haand about 475 g/ha based on the total amount of active ingredients inthe composition. Azoxystrobin is applied at a rate of between about 100g/ha and about 375 g/ha and the compound of Formula I is applied at arate between about 10 g/ha and about 100 g/ha. Pyraclostrobin is appliedat a rate of between about 50 g/ha and about 250 g/ha and the compoundof Formula I is applied at a rate between about 10 g/ha and about 100g/ha.

The compositions comprising the compound of Formula I and a carboxamideSDHI fungicide can be applied at an application rate of between about 35g/ha and about 400 g/ha based on the total amount of active ingredientsin the composition. Fluxapyroxad is applied at a rate of between about45 g/ha and about 200 g/ha and the compound of Formula I is applied at arate between about 10 g/ha and about 100 g/ha. Benzovindiflupyr isapplied at a rate of between about 25 g/ha and about 300 g/ha and thecompound of Formula I is applied at a rate between about 10 g/ha andabout 100 g/ha.

The compositions comprising the compound of Formula I and chlorothalonilcan be applied at an application rate of between about 1010 g/ha andabout 2600 g/ha based on the total amount of active ingredients in thecomposition. Chlorothalonil is applied at a rate of between about 1000g/ha and about 2500 g/ha and the compound of Formula I is applied at arate between about 10 g/ha and about 100 g/ha.

The components of the synergistic mixture described herein can beapplied either separately or as part of a multipart fungicidal system.

The synergistic mixture of the present disclosure can be applied inconjunction with one or more other fungicides to control a wider varietyof undesirable diseases. When used in conjunction with otherfungicide(s), the presently claimed compounds may be formulated with theother fungicide(s), tank mixed with the other fungicide(s) or appliedsequentially with the other fungicide(s). Such other fungicides mayinclude 2-(thiocyanatomethylthio)-benzothiazole, 2-phenylphenol,8-hydroxyquinoline sulfate, ametoctradin, amisulbrom, antimycin,Ampelomyces quisqualis, azaconazole, Bacillus subtilis, Bacillussubtilis strain QST713, benalaxyl, benomyl, benthiavalicarb-isopropyl,benzylaminobenzene-sulfonate (BABS) salt, bicarbonates, biphenyl,bismerthiazol, bitertanol, bixafen, blasticidin-S, borax, Bordeauxmixture, boscalid, bromuconazole, bupirimate, calcium polysulfide,captafol, captan, carbendazim, carboxin, carpropamid, carvone,chlazafenone, chloroneb, chlozolinate, Coniothyrium minitans, copperhydroxide, copper octanoate, copper oxychloride, copper sulfate, coppersulfate (tribasic), cuprous oxide, cyazofamid, cyflufenamid, cymoxanil,cyproconazole, cyprodinil, dazomet, debacarb, diammoniumethylenebis-(dithiocarbamate), dichlofluanid, dichlorophen, diclocymet,diclomezine, dichloran, diethofencarb, difenoconazole, difenzoquat ion,diflumetorim, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M,dinobuton, dinocap, diphenylamine, dipymetitrone, dithianon, dodemorph,dodemorph acetate, dodine, dodine free base, edifenphos, enestrobin,enestroburin, ethaboxam, ethoxyquin, etridiazole, famoxadone,fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil,fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin, fentinacetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil,fluindapyr, flumorph, fluopicolide, fluopyram, fluoroimide,fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil,flutolanil, flutriafol, folpet, formaldehyde, fosetyl,fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, guazatine,guazatine acetates, GY-81, hexachlorobenzene, hexaconazole, hymexazol,imazalil, imazalil sulfate, imibenconazole, iminoctadine, iminoctadinetriacetate, iminoctadine tris(albesilate), iodocarb, ipconazole,ipfenpyrazolone, iprobenfos, iprodione, iprovalicarb, isofetamide,isoprothiolane, isopyrazam, isotianil, kasugamycin, kasugamycinhydrochloride hydrate, kresoxium-methyl, laminarin, mancopper, mancozeb,mandipropamid, maneb, mefenoxam, mepanipyrim, mepronil, meptyl-dinocap,mercuric chloride, mercuric oxide, mercurous chloride, metalaxyl,metalaxyl-M, metam, metam-ammonium, metam-potassium, metam-sodium,metconazole, methasulfocarb, methyl iodide, methyl isothiocyanate,metiram, metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam,nitrothal-isopropyl, nuarimol, octhilinone, ofurace, oleic acid (fattyacids), orysastrobin, oxadixyl, oxathiapiprolin, oxine-copper,oxpoconazole fumarate, oxycarboxin, pefurazoate, penconazole,pencycuron, penflufen, pentachlorophenol, pentachlorophenyl laurate,penthiopyrad, phenylmercury acetate, phosphonic acid, phthalide,picoxystrobin, polyoxin B, polyoxins, polyoxorim, potassium bicarbonate,potassium hydroxyquinoline sulfate, probenazole, prochloraz,procymidone, propamocarb, propamocarb hydrochloride, propiconazole,propineb, proquinazid, pydiflumetofen, pyrametostrobin, pyraoxystrobin,pyraziflumid, pyrazophos, pyribencarb, pyributicarb, pyrifenox,pyrimethanil, pyriofenone, pyroquilon, quinoclamine, quinoxyfen,quintozene, Reynoutria sachalinensis extract, sedaxane, silthiofam,simeconazole, sodium 2-phenylphenoxide, sodium bicarbonate, sodiumpentachlorophenoxide, spiroxamine, sulfur, SYP-Z048, tar oils,tebuconazole, tebufloquin, tecnazene, tetraconazole, thiabendazole,thifluzamide, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl,tolylfluanid, triadimefon, triadimenol, triazoxide, tricyclazole,tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole,validamycin, valifenalate, valiphenal, vinclozolin, zineb, ziram,zoxamide, Candida oleophila, Fusarium oxysporum, Gliocladium spp.,Phlebiopsis gigantea, Streptomyces griseoviridis, Trichoderma spp.,(RS)—N-(3,5-dichlorophenyl)-2-(methoxymethyl)-succinimide,1,2-dichloropropane, 1,3-dichloro-1,1,3,3-tetrafluoroacetone hydrate,1-chloro-2,4-dinitronaphthalene, 1-chloro-2-nitropropane,2-(2-heptadecyl-2-imidazolin-1-yl)ethanol,2,3-dihydro-5-phenyl-1,4-dithi-ine 1,1,4,4-tetraoxide,2-methoxyethylmercury acetate, 2-methoxyethylmercury chloride,2-methoxyethylmercury silicate, 3-(4-chlorophenyl)-5-methylrhodanine,4-(2-nitroprop-1-enyl)phenyl thiocyanateme, aminopyrifen, ampropylfos,anilazine, azithiram, barium polysulfide, Bayer 32394, benodanil,benquinox, bentaluron, benzamacril; benzamacril-isobutyl, benzamorf,binapacryl, bis(methylmercury) sulfate, bis(tributyltin) oxide,buthiobate, cadmium calcium copper zinc chromate sulfate, carbamorph,CECA, chlobenthiazone, chloraniformethan, chlorfenazole, chlorquinox,climbazole, copper bis(3-phenylsalicylate), copper zinc chromate,cufraneb, cupric hydrazinium sulfate, cuprobam, cyclafuramid,cypendazole, cyprofuram, decafentin, dichlobentiazox, dichlone,dichlozoline, diclobutrazol, dimethirimol, dinocton, dinosulfon,dinoterbon, dipyrithione, ditalimfos, dodicin, drazoxolon, EBP, ESBP,etaconazole, etem, ethirim, fenaminosulf, fenapanil, fenitropan,fluindapyr, fluopimomide, fluotrimazole, furcarbanil, furconazole,furconazole-cis, furmecyclox, furophanate, glyodine, griseofulvin,halacrinate, Hercules 3944, hexylthiofos, ICIA0858, inpyrfluxam,ipfentrifluconazole, ipflufenoquin, isoflucypram, isopamphos,isovaledione, mandestrobin, mebenil, mecarbinzid, mefentrifluconazole,metazoxolon, methfuroxam, methylmercury dicyandiamide, metsulfovax,metyltetraprole, milneb, mucochloric anhydride, myclozolin,N-3,5-dichlorophenyl-succinimide, N-3-nitrophenylitaconimide, natamycin,N-ethylmercurio-4-toluenesulfonanilide, nickelbis(dimethyldithiocarbamate), OCH, phenylmercurydimethyldithiocarbamate, phenylmercury nitrate, phosdiphen, prothiocarb;prothiocarb hydrochloride, picarbutrazox, pydiflumetofen, pyracarbolid,pyrapropoyne, pyridachlometyl, pyridinitril, pyroxychlor, pyroxyfur,quinacetol; quinacetol sulfate, quinazamid, quinconazole, quinofumelin,rabenzazole, salicylanilide, SSF-109, sultropen, tecoram, thiadifluor,thicyofen, thiochlorfenphim, thiophanate, thioquinox, tioxymid,triamiphos, triarimol, triazbutil, trichlamide, urbacid, zarilamid, andany combinations thereof.

The compositions of the present disclosure are preferably applied in theform of a formulation comprising a composition of (a) a compound ofFormula I and (b) at least one fungicide selected from the groupconsisting of epoxiconazole, prothioconazole, azoxystrobin,pyraclostrobin, fluxapyroxad, benzovindiflupyr, and chlorothalonil,together with a phytologically acceptable carrier.

Concentrated formulations can be dispersed in water, or another liquid,for application, or formulations can be dust-like or granular, which canthen be applied without further treatment. The formulations are preparedaccording to procedures which are conventional in the agriculturalchemical art, but which are novel and important because of the presencetherein of a synergistic composition.

The formulations that are applied most often are aqueous suspensions oremulsions. Either such water-soluble, water-suspendable, or emulsifiableformulations are solids, usually known as wettable powders, or liquids,usually known as emulsifiable concentrates, aqueous suspensions, orsuspension concentrates. The present disclosure contemplates allvehicles by which the synergistic compositions can be formulated fordelivery and use as a fungicide.

As will be readily appreciated, any material to which these synergisticcompositions can be added may be used, provided they yield the desiredutility without significant interference with the activity of thesesynergistic compositions as antifungal agents.

Wettable powders, which may be compacted to form water-dispersiblegranules, comprise an intimate mixture of the synergistic composition, acarrier and agriculturally acceptable surfactants. The concentration ofthe synergistic composition in the wettable powder is usually from about10% to about 90% by weight, more preferably about 25% to about 75% byweight, based on the total weight of the formulation. In the preparationof wettable powder formulations, the synergistic composition can becompounded with any of the finely divided solids, such as prophyllite,talc, chalk, gypsum, Fuller's earth, bentonite, attapulgite, starch,casein, gluten, montmorillonite clays, diatomaceous earths, purifiedsilicates or the like. In such operations, the finely divided carrier isground or mixed with the synergistic composition in a volatile organicsolvent. Effective surfactants, comprising from about 0.5% to about 10%by weight of the wettable powder, include sulfonated lignins,naphthalenesulfonates, alkylbenzenesulfonates, alkyl sulfates, andnon-ionic surfactants, such as ethylene oxide adducts of alkyl phenols.

Emulsifiable concentrates of the synergistic composition comprise aconvenient concentration, such as from about 10% to about 50% by weight,in a suitable liquid, based on the total weight of the emulsifiableconcentrate formulation. The components of the synergistic compositions,jointly or separately, are dissolved in a carrier, which is either awater-miscible solvent or a mixture of water-immiscible organicsolvents, and emulsifiers. The concentrates may be diluted with waterand oil to form spray mixtures in the form of oil-in-water emulsions.Useful organic solvents include aromatics, especially the high-boilingnaphthalenic and olefinic portions of petroleum such as heavy aromaticnaphtha. Other organic solvents may also be used, such as, for example,terpenic solvents, including rosin derivatives, aliphatic ketones, suchas cyclohexanone, and complex alcohols, such as 2-ethoxyethanol.

Emulsifiers which can be advantageously employed herein can be readilydetermined by those skilled in the art and include various nonionic,anionic, cationic and amphoteric emulsifiers, or a blend of two or moreemulsifiers. Examples of nonionic emulsifiers useful in preparing theemulsifiable concentrates include the polyalkylene glycol ethers andcondensation products of alkyl and aryl phenols, aliphatic alcohols,aliphatic amines or fatty acids with ethylene oxide, propylene oxidessuch as the ethoxylated alkyl phenols and carboxylic esters solubilizedwith the polyol or polyoxyalkylene. Cationic emulsifiers includequaternary ammonium compounds and fatty amine salts. Anionic emulsifiersinclude the oil-soluble salts (e.g., calcium) of alkylaryl sulfonicacids, oil-soluble salts or sulfated polyglycol ethers and appropriatesalts of phosphated polyglycol ether.

Representative organic liquids which can be employed in preparing theemulsifiable concentrates of the present disclosure are the aromaticliquids such as xylene, propyl benzene fractions, or mixed naphthalenefractions, mineral oils, substituted aromatic organic liquids such asdioctyl phthalate, kerosene, dialkyl amides of various fatty acids,particularly the dimethyl amides of fatty glycols and glycol derivativessuch as the n-butyl ether, ethyl ether or methyl ether of diethyleneglycol, and the methyl ether of triethylene glycol. Mixtures of two ormore organic liquids are also often suitably employed in the preparationof the emulsifiable concentrate. The preferred organic liquids arexylene, and propyl benzene fractions, with xylene being most preferred.The surface-active dispersing agents are usually employed in liquidformulations and in the amount of from 0.1 to 20 percent by weight ofthe combined weight of the dispersing agent with the synergisticcompositions. The formulations can also contain other compatibleadditives, for example, plant growth regulators and other biologicallyactive compounds used in agriculture.

Aqueous suspensions comprise suspensions of one or more water-insolublecompounds, dispersed in an aqueous vehicle at a concentration in therange from about 5% to about 70% by weight, based on the total weight ofthe aqueous suspension formulation. Suspensions are prepared by finelygrinding the components of the synergistic combination either togetheror separately, and vigorously mixing the ground material into a vehiclecomprised of water and surfactants chosen from the same types discussedabove. Other ingredients, such as inorganic salts and synthetic ornatural gums, may also be added to increase the density and viscosity ofthe aqueous vehicle. It is often most effective to grind and mix at thesame time by preparing the aqueous mixture and homogenizing it in animplement such as a sand mill, ball mill, or piston-type homogenizer.

The synergistic composition may also be applied as a granularformulation, which is particularly useful for applications to the soil.Granular formulations usually contain from about 0.5% to about 10% byweight of the compounds, based on the total weight of the granularformulation, dispersed in a carrier which consists entirely or in largepart of coarsely divided attapulgite, bentonite, diatomite, clay or asimilar inexpensive substance. Such formulations are usually prepared bydissolving the synergistic composition in a suitable solvent andapplying it to a granular carrier which has been preformed to theappropriate particle size, in the range of from about 0.5 to about 3millimeters (mm). Such formulations may also be prepared by making adough or paste of the carrier and the synergistic composition, andcrushing and drying to obtain the desired granular particle.

Dusts containing the synergistic composition are prepared simply byintimately mixing the synergistic composition in powdered form with asuitable dusty agricultural carrier, such as, for example, kaolin clay,ground volcanic rock, and the like. Dusts can suitably contain fromabout 1% to about 10% by weight of the synergistic composition/carriercombination.

The formulations may contain agriculturally acceptable adjuvantsurfactants to enhance deposition, wetting and penetration of thesynergistic composition onto the target crop and organism. Theseadjuvant surfactants may optionally be employed as a component of theformulation or as a tank mix. The amount of adjuvant surfactant willvary from 0.01 percent to 1.0 percent volume/volume (v/v) based on aspray-volume of water, preferably 0.05 to 0.5 percent. Suitable adjuvantsurfactants include ethoxylated nonyl phenols, ethoxylated synthetic ornatural alcohols, salts of the esters or sulfosuccinic acids,ethoxylated organosilicones, ethoxylated fatty amines and blends ofsurfactants with mineral or vegetable oils.

The formulations may optionally include combinations that can compriseat least 1% by weight of one or more of the synergistic compositionswith another pesticidal compound. Such additional pesticidal compoundsmay be fungicides, insecticides, nematicides, miticides,arthropodicides, bactericides or combinations thereof that arecompatible with the synergistic compositions of the present disclosurein the medium selected for application, and not antagonistic to theactivity of the present compounds. Accordingly, in such embodiments theother pesticidal compound is employed as a supplemental toxicant for thesame or for a different pesticidal use. The pesticidal compound and thesynergistic composition can generally be mixed together in a weightratio of from 1:100 to 100:1.

The present disclosure includes within its scope methods for the controlor prevention of fungal attack. These methods comprise applying to thelocus of the fungus, or to a locus in which the infestation is to beprevented (for example applying to wheat or barley plants), afungicidally effective amount of the synergistic composition. Thesynergistic composition is suitable for treatment of various plants atfungicidal levels, while exhibiting low phytotoxicity. The synergisticcomposition is useful in a protectant or eradicant fashion. Thesynergistic composition is applied by any of a variety of knowntechniques, either as the synergistic composition or as a formulationcomprising the synergistic composition. For example, the synergisticcompositions may be applied to the roots, seeds or foliage of plants forthe control of various fungi, without damaging the commercial value ofthe plants. The synergistic composition is applied in the form of any ofthe generally used formulation types, for example, as solutions, dusts,wettable powders, flowable concentrates, or emulsifiable concentrates.These materials are conveniently applied in various known fashions.

The synergistic composition has been found to have significantfungicidal effect, particularly for agricultural use. The synergisticcomposition is particularly effective for use with agricultural cropsand horticultural plants, or with wood, paint, leather or carpetbacking.

In particular, the synergistic composition is effective in controlling avariety of undesirable fungi that infect useful plant crops. Thesynergistic composition may be used against a variety of Ascomycete andBasidiomycete fungi, including for example the following representativefungi species: barley leaf scald (Rhynchosporium secalis); barleyRamularia leaf spot (Ramularia collo-cygni); barley net blotch(Pyrenophora teres); barley powdery mildew (Blumeria graminis f. sp.hordei); wheat powdery midlew (Blumeria graminis f. sp. tritici); wheatbrown rust (Puccinia triticina); stripe rust of wheat (Pucciniastriiformis); leaf blotch of wheat (Zymoseptoria tritici); glume blotchof wheat (Parastagonospora nodorum); leaf spot of sugar beets(Cercospora beticola); leaf spot of peanut (Mycosphaerella arachidis);cucumber anthracnose (Colletotrichum lagenarium); cucumber powderymildew (Erysiphe cichoracearum); watermelon stem gummy blight (Didymellabryoniae); apple scab (Venturia inaequalis); apple powdery mildew(Podosphaera leucotricha); grey mold (Botrytis cinerea); Sclerotiniawhite mold (Sclerotinia sclerotiorum); grape powdery mildew (Erysiphenecator); early blight of tomato (Alternaria solani); rice blast(Pyricularia oryzae); brown rot of stone fruits (Monilinia fructicola)and black sigatoka disease of banana (Mycosphaerella fijiensis). It willbe understood by those in the art that the efficacy of the synergisticcompositions for one or more of the foregoing fungi establishes thegeneral utility of the synergistic compositions as fungicides.

The synergistic compositions have a broad range of efficacy as afungicide. The exact amount of the synergistic composition to be appliedis dependent not only on the relative amounts of the components, butalso on the particular action desired, the fungal species to becontrolled, and the stage of growth thereof, as well as the part of theplant or other product to be contacted with the synergistic composition.Thus, formulations containing the synergistic composition may not beequally effective at similar concentrations or against the same fungalspecies.

The synergistic compositions are effective in use with plants in adisease-inhibiting and phytologically acceptable amount. The term“disease-inhibiting and phytologically acceptable amount” refers to anamount of the synergistic composition that kills or inhibits the plantdisease for which control is desired, but is not significantly toxic tothe plant. The exact concentration of synergistic composition requiredvaries with the fungal disease to be controlled, the type of formulationemployed, the method of application, the particular plant species,climate conditions, and the like.

The present compositions can be applied to fungi or their locus by theuse of conventional ground sprayers, granule applicators, and by otherconventional means known to those skilled in the art.

The following examples are provided for illustrative purposes and shouldnot be construed as limitations to the disclosure.

Examples

Evaluation of Protectant Activity of Fungicide Mixtures vs. Barley Scald(Rhynchosporium secalis; Bayer code:RHYNSE):

Barley seedlings (variety Harrington) were propagated in soil-less Metromix, with each pot having 8 to 12 plants, and used in the test whenfirst leaf was fully emerged. Treatments consisted of fungicidecompounds epoxiconazole, prothioconazole, azoxystrobin, pyraclostrobin,benzovindiflupyr, fluxapyroxad, and chlorothalonil, either usingindividually or as two-way mixture with the compound of Formula I.

The compounds were tested as technical grade material formulated inacetone, and spray solutions contained 10% acetone and 100 ppm TritonX-100. Fungicide solutions were applied onto plants using an automatedbooth sprayer, which utilized two 6218-1/4 JAUPM spray nozzles operatingat 20 pounds per square inch (psi) set at opposing angles to cover bothleaf surfaces. All sprayed plants were allowed to air dry prior tofurther handling. Control plants were sprayed in the same manner withthe solvent blank.

Test plants were inoculated with an aqueous spore suspension ofRhyncosporium secalis 1 day after fungicide treatments (1-day protectanttest). After inoculation the plants were kept in 100% relative humidityfor two days to permit spores to germinate and infect the leaf. Theplants were then transferred to a greenhouse for disease to develop.When disease fully developed on untreated plants, disease severity onthe first leaf of the seedlings was assessed and activity wasrepresented by percent of leaf area free of RHYNSE infection relative tothe untreated plants.

Colby's equation was used to determine the fungicidal effects expectedfrom the mixtures. (See Colby, S. R. Calculation of the synergistic andantagonistic response of herbicide combinations. Weeds 1967, 15, 20-22.)

The following equation was used to calculate the expected activity ofmixtures containing two active ingredients, A and B:

Expected = A + B − (A × B/100)

-   -   A=observed efficacy of active component A at the same        concentration as used in the mixture;    -   B=observed efficacy of active component B at the same        concentration as used in the mixture.

Synergistic interactions between compound I and other fungicides weredetected in protectant assays vs. RHYNSE (Table 1).

TABLE 1 Synergistic Interactions of the Compound of Formula I and OtherFungicides in a 1-Day Protectant (1 DP) Rhynchosporium secalis (RHYNSE)Assay. RHYNSE* Synergism Composition Rates (ppm)* Observed* Expected*Factor* Epoxiconazole + Compound I 0.097 + 1.56  46 14 3.38Prothioconazole + Compound I 1.56 + 1.56 67 14 4.92 Prothioconazole +Compound I 0.78 + 0.78 29 21 1.40 Azoxystrobin + Compound I 3.12 + 3.1295 57 1.67 Azoxystrobin + Compound I 12.5 + 1.56 93 38 2.47Azoxystrobin + Compound I 6.25 + 1.56 93 14 6.83 Azoxystrobin + CompoundI 3.12 + 1.56 73 19 3.85 Azoxystrobin + Compound I 12.5 + 0.78 90 283.23 Azoxystrobin + Compound I 3.12 + 0.78 56 6 9.00 Pyraclostrobin +Compound I 0.48 + 3.12 99 61 1.64 Pyraclostrobin + Compound I 0.24 +3.12 99 62 1.60 Pyraclostrobin + Compound I 0.12 + 3.12 96 54 1.78Pyraclostrobin + Compound I 0.48 + 1.56 94 26 3.69 Pyraclostrobin +Compound I 0.24 + 1.56 92 28 3.28 Pyraclostrobin + Compound I 0.12 +1.56 91 14 6.71 Pyraclostrobin + Compound I 0.48 + 0.78 80 14 5.79Pyraclostrobin + Compound I 0.24 + 0.78 67 17 4.00 Fluxapyroxad +Compound I 0.12 + 3.12 81 54 1.50 Fluxapyroxad + Compound I 0.24 + 1.5679 14 5.85 Fluxapyroxad + Compound I 0.12 + 1.56 29 14 2.15Benzovindiflupyr + Compound I   2 + 1.56 79 49 1.62 Chlorothalonil +Compound I  25 + 3.12 88 54 1.62 Chlorothalonil + Compound I  50 + 1.5698 46 2.12 Chlorothalonil + Compound I  25 + 1.56 70 14 5.17Chlorothalonil + Compound I 12.5 + 1.56 25 14 1.85 Chlorothalonil +Compound I  50 + 0.78 81 38 2.17 *RHYNSE = Barley scald; Rhynchosporiumsecalis *Observed = Observed percent disease control at the test rates*Expected = Percent disease control expected as predicted by the Colbyequation *ppm = Parts per million *Synergism factor = Observed/Expected

What is claimed:
 1. A synergistic fungicidal mixture, comprising: afungicidally effective amount of the compound of Formula I,(S)-1,1-bis(4-fluorophenyl)propan-2-yl(3-acetoxy-4-methoxypicolinoyl)-L-alaninate:

and at least one additional fungicide selected from the group consistingof sterol biosynthesis inhibitors, respiration inhibitors, andmulti-site action inhibitors.
 2. The mixture of claim 1 wherein thesterol biosynthesis inhibitor (SBI) is selected from the groupconsisting of epoxiconazole and prothioconazole.
 3. The mixture of claim2 wherein a concentration ratio of the compound of Formula I toepoxiconazole is about 16:1.
 4. The mixture of claim 2 wherein aconcentration ratio of the compound of Formula I to prothioconazole isabout 1:1.
 5. The mixture of claim 1 wherein the respiration inhibitoris selected from the group consisting of azoxystrobin andpyraclostrobin.
 6. The mixture of claim 5 wherein a concentration ratioof the compound of Formula I to azoxystrobin is from about 1:1 to about1:16.
 7. The mixture of claim 5 wherein a concentration ratio of thecompound of Formula I to pyraclostrobin is from about 26:1 to about1.6:1.
 8. The mixture of claim 1 wherein at least the respirationinhibitor is selected from the group consisting of fluxapyroxad andbenzovindiflupyr.
 9. The mixture of claim 8 wherein a concentrationratio of the compound of Formula I to fluxapyroxad is from about 26:1 toabout 6.5:1.
 10. The mixture of claim 8 wherein a concentration ratio ofthe compound of Formula I to benzovindiflupyr is about 1:1.3.
 11. Themixture of claim 1 wherein the multi-site inhibitor is chlorothalonil.12. The mixture of claim 11 wherein a concentration ratio of thecompound of Formula I to chlorothalonil is from about 1:8 to about 1:64.13. The mixture of claims 1-12, wherein the mixture provides control ofa fungal pathogen, and the pathogen is the causal agent of barley scald(Rhynchosporium secalis).
 14. A synergistic, fungicidal compositioncomprising of a fungicidally effective amount of the mixtures of claims1-12 and an agriculturally acceptable carrier.